Water-insoluble monoazo-dyestuffs



United States Patent 3,250,763 WATER-INSOLUBLE MONOAZO-DYESTUFFS Helmut Gies, Hofheim, Taunus, and Helmut Lindner and Arthur Siebert, Frankfurt am Main, Germany, assrguors to Farbwerke Hoechst Aktiengesellschaft vormals Meister Lucius & Bruning, Frankfurt am Main, Germany, a corporation of Germany No Drawing. Filed June 18, 1963, Ser. No. 288,626 Claims priority, application Germany, June 23, 1962, F 37,144; Nov. 29, 1962, F 38,422 6 Claims. (Cl. 260-207) The present invention relates to water-insoluble monoazo-dyestufis and to a process for preparing them; more particularly it relates to water-insoluble monoazo-dyestuffs having the general formula 0 Hi4; HC0R,

in which R represents a hydrogen atom or an alkyl radical and R represents an alkyl radical.

It has been found that valuable water-insoluble monoazo-dyestutfs having the general formula 2 NH-CO-CHa in which X represents a hydrogen, chlorine or bromine atom, R represents an alkyl group which may be sub-- stituted by hydroxyl, alkoxy or acyloxy groups, and R represents 'an alkyl, a cyanalkyl, an aralkyl, a B-hydroxyfi-chloropropyl or a ,B-acylethyl radical having the general formula C 1124'; HC OR in which R represents a hydrogen atom or an alkyl radical and R represents an alkyl radical, are obtained by diazotizing amines having the general formula ice in which X is defined as above, and coupling them in an acid medium with coupling components having the general formula NHOOCH3 in which R and R are defined as above.

As diazo components there may be used 2,4-dinitraniline and derivatives thereof substituted in 6-position by a chlorine or a bromine atom. Suitable coupling components are for example 2 n butylamino 4 acetamino 1 ,6 aceto hydroxyphenetole,

2 ethylamino 4 acetamino 1 ,8 aceto hydroxyphenetole,

2 n butylamino 4 acetamino 1 fl methoxy phenetole,

2 iso hexylamino 4 acetamino 1 B methoxyphenetole,

2-6-phenylpropylamino-4-acetamino-l-phenetole,

2-n-butylamino-4-acetamino-l-phenetole,

2-iso-pentylamino-4-acetamino-l-phenetole,

2-iso-hexylamino-4-acetamino-1-phenetole,

2 (3' hydroxy benzylamino) 4 acetamino 1- phenetole,

2- 2-furfurylamino -4-'acetaminol-phenetole,

2-n-propylamino-4-acetamino-l-phenetole,

Z-B-cyanethylamino-4-acetamino-l phenetole or 2 ,8 cyanethylamino 4 acetamino 1 B hydroxyphenetole.

The novel monoazo-dyestuffs obtainable in the process of the present invention dye as dispersion dyestuffs semiand fully synthetic fibers, such as acetate silk and polyethylene terephthalate fibers, violet to blue shades and in admixture with other dyestuffs are suitable for producing black shades. The dyeings obtained are distinguished by a very good fastness to light and, as a rule, also by a good fastness to thermofixation.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto, the parts being by weight unless otherwise stated and the relationship of parts by weight to parts by volume being the same as that of the kilogram to the liter.

Example 1 21.7 parts mol) of 2,4-dinitro-6-chloraniline are diazotized in usual manner in sulfuric acid with nitrosylsulfuric acid. This diazo solution is run, while stirring, into a solution of 31 parts A mol) of Z-n-butylamino- 4-acetamino-113-acetohydroxy-phenetole (obtainable by reductive alkylation from 2-nitro-4-acetamino-l-B-acetohydroxy-phenetole and n-butanal) in 300 parts of glacial acetic acid to which 1 part of amido-sulfonic acid and 500 parts of ice had been added. The mixture is then diluted with water to about 3000 parts by volume and the pH- value is adjusted to 3 by adding sodium acetate solution.

After about 2 hours the precipitated dyestuif having the formula is filtered off, washed with water until neutral and dried. 50 parts of a dyestulf are obtained which in an aqueous dispersion dyes polyethylene terephthalate fibers dark blue shades. The dyeings possess a very good fastness to light and to sublimation.

Example 2 26.2 parts (V mol) of 2,4-dinitro-6-bromani1ine are diazotized in usual manner in sulfuric acid with nitrosylsulfuric acid. The diazo solution obtained is run, while vigorously stirring, into a solution of 28 parts mol) of 2-n-butylarm'no-4-acetamino-l-p-methoxy-phenetole (obtainable by reductive alkylation from 2-nitro-4- acetamino-l-fi-methoxy-phenetole and n-butanal) in 300 parts 'of glacial acetic acid with the addition of ice. Subsequently the mixture is diluted with water to 3000 parts by volume, and the pH-value is adjusted to 3 by adding sodium acetate solution. After 2 hours the precipitated dyestulf is filtered off, washed with water until neutral and dried. It has the following composition:

N02 IilH-O O-GHz It dyes polyethylene terephthalate fibers dark blue shades. The dyeings possess a very good fastness to light and'to sublimation.

Example 3 dyes polyethylene terepht-halate fabric violet shades. The dyeings possess a very good fastness to light and to subli mation.

Example 4 22.4 parts mol) of 2-nitro-4-acetamino-l-phenetole are dissolved in 150 parts of alcohol and alkylated by reduction with the addition of cinnamic aldehyde in the presence of a Raney nickel catalyst and hydrogen.

After the removal of the catalyst the solvent and the cinnamic aldehyde in excess are distilled off. The residue is dissolved in 200 parts of glacial acetic acid and about 1 part of amidosulfonic acid is added. Into this solution is run, while vigorously stirring, a solution of 21.7 parts A mol) of diazotized 2,4-dinitro-6chloraniline in parts of concentrated sulfuric acid, While simultaneously adding about 800 parts of ice. The mixture is then diluted with Water to about 3000 parts by volume and worked up as described in Example 1. The dyestuff obtained having the formula dyes polyethylene terephthalate fibers pure blue shades. The dyeings possess a very good fastness to light and a good fastness to sublimation.

Example 5 18.3 parts (l mol) of 2,4-dinitraniline are diazotized in usual manner. This diazo solution is run into a solution of 25 parts A mol) 2-n-butylamino-4-acetaminol-phenetole in 200 parts of glacial acetic acid to which ice had been added. After the introduction the mixture is worked up as. described in Example 1. The dyestulf obtained having the formula NH-C nt-ont-onz on,

l 1 N02 un-co-o H,

dyespolyester fibers violet shades. The dyeings possess a very good fastness to light.

Example 6 26.2 parts mol) of 2,4dinitro-6-bromaniline are NO: I\THCO-C 113 on dyes polyethylene terephthalate fibers pure blue shades. T-he dyeings possess a very good fastness to light and a good fastness to sublimation.

The following table contains a certain number of further water-insoluble monazo-dyestufits obtainable in the process of the present invention and having the general formula In the last column of the table the tints of the dyeings are indicated which can be obtained with these dyestuffs on polyester fabric.

The dyestuflf obtained having I is filtered 01f, washed with water until neutral and dried. The dyestufi obtained dyes in an aqueous dispersion, at

blue shades. The dyeings possess a very good fastness to light and to sublimation.

When using instead of the above-mentioned coupling component 2 5-chloro-B-hydroxy-propylarnino-4-acetamino-l-fi-methoxy-phenetole, a dyestufi possessing similarly good properties is obtained.

Example 8 18.3 parts mol) of 2,4-dinitranilene are diazotized in usual manner with nitrosylsulfuric acid. The diazo solution obtained is run, while stirring, into a solution of 28.7 parts mol) of 2-6-chloro-p-hydroxy-propylamino- 4-acetamino-phenetole in 300 parts of glacial acetic acid. Ice is added for cooling. The mixture is then diluted with water to 3000 parts by volume and the pH-value is adjusted to 3 by adding sodium acetate solution. After 2 hours the dyestufi is filtered OE and Washed with Water until neutral. After drying the dyestuif is a violet-black powder which in an aqueous dispersion, at 130 C., dyes polyethylene terephthalate fibers violet shades. The dyeings obtained possess very good fastness properties.

When using instead of the above-mentioned coupling component 2-5-chloro-B-hydroxy-propylarnino-4-acetamino-anisole, a dyestuff possessing similarly good properties ,is obtained.

Example 9 26.2 parts A mol) of 2,4-dinitro-6-bromaniline are diazotized in usual manner with nitrosylsulfuric acid. The diazo solution obtained is run, while stirring, into a solution of 28.7 parts mol) of 2-5-chloro-fl-hydroxyproplyamino 4 acetamino phenetole which had been cooled with ice. The mixture is then diluted slowly with Example 10 21.7 parts of 2,4-dinitro-6-chloraniline are diazotized in usual manner in glacial acetic acid with nitrosysulfuric acid. The diazo solution thus obtained is run, while stirring, into a solution of 26.4 parts of Z-( B-acetyI-ethylamino)-4-acetamino-phenetole in 100 ml. of lN-hydrochloric acid to which 1 part of amidosulfonic acid and 500 parts of ice had been added. The mixture is then diluted with water to about 300 parts by volume and after-stirred for about 2 hours. Subsequently the precipitated dyestufi having the formula no, NH-O oe n.

is filtered off, washed thoroughly with Water, and dried in usual manner. The dyestufl obtained dyes in an aquef ous dispersion, at 120 to 130 C., polyethylene terephthalate fibers navy blue shades. The dyeings possess a very good fastness to light and to sublimination.

When using instead of the above-mentioned coupling component 2-(fi-acetylpropylamino)-4-acetamino phenetole, a dyestufi possessing similarly good properties is obtained.

Example 1 1 18.3 parts of 2,4-dinitraniline are diazotized in usual manner with nitrosylsulfuric acid. The diazo solution obtained is run, while stirring, into a solution of 30 parts of 2-(B-acetyl-ethylamino)-4-acetarnino phenetole combined with hydrochloric acid in water. Ice is added for cooling. The mixture is then diluted with water to 300 parts by.volume and after-stirred for 2 hours. Subsequently, the precipitated dyestufI' is filtered off with suction, washed until neutral and dried in usual manner. After drying the dyestufi is a blue-black powder which in an aqueous dispersion, at 130 C., dyes polyethylene terephthalate fibers violet shades. The dyeings possess very good fastness properties.

When using instead of the above-mentioned coupling component Z-(B-propionylpropylamino) 4 acetaminophenetole, a dyestuif possessing similarly good properties is obtained.

Example 1 26.2 parts of 2,4-dinitro-6-broaniline are diazotized in usual manner with nitrosylsulfuric acid. The diazo solu- :tion obtained is run, while stirring vigorously, into a 7 solution of 30 parts of Z-(fi-acetylethyl'amino)-4-acetamino-phenetole combined with hydrochloric acid which had been cooled with ice. The mixture is diluted slowly with water to 3000' parts by volume and the precipitated dyestuff is filtered off with suction after 2 hours, washed until neutral and dried. It is a blue-black powder which in an aqueous dispersion, at C., dyes polyethylene terephthalate fibers dark blue shades. The dyeings possess a very good fastness to light and to sublimation.

When using instead of the above-mentioned coupling component 2 (fi-isobutyro-ethylamino) 4 acetaminophenetole, a dyestuff possessing similarly good properties is obtained.

We claim: 1. A water-insoluble dyestuff of the formula N..@ ...N@ NH.. I

l lo 2 NHC O 0 H3 wherein X represents chlorine or bromine, R represents lower alkyl or CH CH OCO-lower. alkyl groups, R represents lower alkyl, phenyl-lower alkyl, ,3- hydroxy-y chloropropyl or -CH CH CO-lower alkyl groups, and wherein at most one lower alkyl group.

2. The water-insoluble monoazo-dy'estufi having the formula I 3. The water-insoluble mono-azo-dyestufi having the formula 4. The water-insoluble monoazo-dyestufi having the formula NO: NHC O-GHa 5. The water-insoluble monoazo-dyestufi having the formula 6. The water-insoluble monoazo-dyestuff having the formula NHG nho u onron.

References Cited by the Examiner UNITED STATES PATENTS 6/1937 Senn 260207 CHARLES B. PARKER, Primary Examiner. IRVING MARCUS, JOSEPH P. BRUST, Examiners.

REYNOLD I. FINNEGAN, DONALD M. PAPUGA,

Assistant Examiners.

of R and R is a 

1. A WATER-INSOLUBLE DYESTUFF OF THE FORMULA 